Chlorine dioxide is utilized in a variety of bleaching operations, particularly in the bleaching of cellulosic fibrous material, such as, wood pulp. In U.S. Pat. Nos. 3,895,100 and 3,975,506 assigned to the assignee of this application, the disclosures of which are incorporated herein by reference, there is disclosed a chlorine dioxide generating process and equipment therefor wherein chlorine dioxide is formed in a generally cylindrical upright reaction vessel by reduction of an alkali metal chlorate, usually sodium chlorate, with chloride ions in an aqueous acid reaction medium, in accordance with the equation: EQU ClO.sub.3.sup.- +Cl.sup.- +2H.sup.+ .fwdarw.ClO.sub.2 +1/2Cl.sub.2 +H.sub.2 O
The reaction medium in the generator is maintained at its boiling point, generally about 25.degree. to about 90.degree. C., under a subatmospheric pressure, generally about 20 to about 400 mm Hg, to cause the deposition of a by-product salt from the reaction medium in the generation vessel once saturation has been achieved after start-up and to remove the chlorine dioxide and chlorine in gaseous admixture with steam.
The by-product salt which is precipitated depends on the acid used in the reaction medium, the by-product being a sodium sulphate when sulphuric acid is used and sodium chloride and/or hydrogen chloride provide the chloride ion reducing agent, and the by-product being sodium chloride when hydrochloric acid is used and also provides the reducing agent.
When sulphuric acid is used, the sodium sulphate may be in an acidic or neutral form depending on the total acid normality of the generator, with a neutral salt generally being obtained at total acid normalities of about 2 to about 5 normal and acid salts being obtained at higher values usually up to about 12 normal.
When the total acid normality of a sulphuric acid based system is such as to produce neutral sodium sulphate, it is preferred to use a reaction temperature above about 30.degree. C. in order to obtain the anhydrous salt.
When hydrochloric acid is used, the actual hydrogen ion concentration in the reaction medium is maintained in the range of about 0.05 to about 0.3 normal. The term "actual hydrogen ion concentration", as used herein, is the value determined by a pH meter calibrated on an 0.1 normal solution of hydrochloric acid on the assumption that such a solution is 100% dissociated at this concentration.
As described in the above-mentioned patents, the solid by-product is removed as a slurry in reaction medium from the generator vessel, sodium chlorate solution is mixed therewith, the mixture is recycled through a reboiler wherein the mixture is heated to the reaction temperature and forwarded to the reaction vessel after the addition of acid to the heated mixture. A portion of the slurry is withdrawn prior to the reboiler for crystal separation.
The heated mixture from the reboiler is passed through a venturi-like pipe which exerts sufficient back pressure on the mixture in the reboiler to prevent boiling therein, acid in concentrated form is introduced to the collar of the venturi and the resultant reaction mixture is allowed to expand at low acceleration to permit boiling and gaseous product formation to occur evenly and gradually and thereby avoid bumping and vibration, so that a fluid mixture of solid phase, liquid phase and gaseous phase is formed and this fluid mixture enters the generator generally radially of the generator above the liquid level therein through a curved pipe joining the downstream end of the venturi-like pipe and the generation vessel inlet.
While this prior art procedure represents an excellent commercially-viable chlorine dioxide generating system having many advantages over prior art arrangements, as described in the above-mentioned patents, it has been found that entrainment of liquid and solid phases in the gaseous phase occurs, necessitating a considerable vapor space in the generator to achieve separation of the entrained material by the action of gravitational forces, otherwise the entrained material passes out of the generator with the removed gases, presenting problems in later-processing of the gases and is considered undesirable.
Additionally, it has been found that the radial entry of the fluid mixture causes considerable splashing of reaction medium and entrainment of gaseous material in the reaction medium. A considerable reaction medium volume is required to permit the entrained gaseous material to disengage from the reaction medium, otherwise chlorine dioxide and chlorine exit the generator in the by-product slurry stream and cause considerable difficulties upon exposure to atmosphere at the solid by-product filter.
At the time of the making of the inventions of the above-mentioned U.S. Pat. Nos. 3,895,100 and 3,975,506 chlorine dioxide generators were constructed from glass fibre reinforced plastics (FRP's) and typical dimensions of a 10 ton per day chlorine dioxide generator were a diameter of about 9 ft, a vapor height of about 10 ft, and an overall height of about 35 ft, giving a total volume of about 2000 cu. ft and a vapor space volume of about 650 cu. ft. These dimensions were adequate to permit the desired disentrainments.
However, FRP's have been found not to be wholly satisfactory as a material of construction for chlorine dioxide generators owing to unsatisfactory wear characteristics and titanium has replaced FRP's as the material of construction, as a result of its high corrosion and wear resistance and excellent constructional qualities. In view of the high cost of this metal, there has been a distinct trend to provide smaller volume chlorine dioxide generators and design parameters for a 10 ton/day chlorine dioxide generator constructed of titanium typically result in a diameter of about 7 ft, an overall height of about 20 ft and a vapor space height of about 6 ft. The overall volume of the generator thereby is decreased to about 750 cu. ft and the vapor space volume is decreased to about 230 cu. ft, i.e., approximately 1/3rd of the respective volumes of the same capacity generator constructed of FRP.
The large decrease in vapor space and reaction medium volumes renders the gas-liquid entrainment problems noted above acute and no longer permits the radial-type entry of recycled fluid mixture to the generator without encountering the difficulties of passage out of the generator of entrained reaction medium with gaseous phase and passage out of the generator of entrained gaseous phase with reaction medium.
One prior art suggestion for overcoming the problem of entrainment of liquid phase in gaseous phase without the use of excessive vapor space is to use an internal demister, as described, for example, in U.S. Pat. No. 4,079,123, but such demisters, consisting usually of wire mesh through which the vapor phase passes and on which the liquid droplets impinge, are prone to clogging especially since the solid phase is also present, and hence must be cleaned frequently if chlorine dioxide production is to be sustained. As far as we are aware there have been no prior art suggestions for overcoming the problem of entrainment of gaseous phase in the reaction medium without the use of excessive reaction medium volume.